Stability, electronic and catalytic properties of ConMoP(n = 1 ~ 5) clusters: A DFT study

Abstract

Context: The investigation of the stability, electronic properties, and catalytic activity of clusters Co_nMoP holds significant applications and implications in catalyst design, materials science, energy conversion and storage, and environmental protection. The study aims to delve into the unique features of the clusters Co_nMoP(n = 1 ~ 5), aiming to drive advancements in these related fields. The results obtained from the analysis revealed the stable configurations of the ten clusters, primarily characterized by steric structures. Furthermore, the energy of the clusters was found to increase continuously during growth, as indicated by calculations of atomic fragmentation energy and atomic binding energy. The researchers conducted an analysis of the Natural Population Analysis(NPA) charge, which revealed that Co atoms acted as electron donors, while P and Mo atoms acted as electron acceptors within the clusters. Additionally, an examination of the electrostatic potential indicated that Co and Mo atoms displayed nucleophilic tendencies, while P atoms exhibited electrophilic characteristics. Moreover, the density of states curves, HOMO and LUMO orbitals, and Kooperman's theorem were applied to the clusters Co_nMoP(n = 1 ~ 5).Through this study, a deeper understanding of the properties and behavior of clusters Co_nMoP has been achieved, shedding light on their potential as catalysts. The findings contribute to the existing knowledge of these clusters and provide a basis for further research and exploration in this field.

Methods: In this study, we employed the clusters Co_nMoP(n = 1 ~ 5) to simulate the local structure of the material, enabling us to investigate the stability, electronic properties, and catalytic properties influenced by the metal atoms. By systematically increasing the number of metal atoms and expanding the cluster size, we explored the variations in these properties. Density functional theory (DFT) calculations were performed using the B3LYP hybrid functional implemented in the Gaussian09 software package. The clusters Co_nMoP(n = 1 ~ 5) underwent optimization calculations and vibrational analysis at the def2-tzvp quantization level, resulting in optimized configurations with different spin multiplet degrees. For data characterization and graphical representation of the stability, electronic properties, and catalytic properties of the optimized configurations, we utilized a range of computational tools. Specifically, the quantum chemistry software GaussView, wave function analysis software Multiwfn were employed. Through the comprehensive utilization of these computational tools, we gained valuable insights into the stability, electronic properties, and catalytic properties of the clusters Co_nMoP(n = 1 ~ 5) and their dependence on different metal atoms.

Keywords: Clusters ConMoP; Density of states map; Fragmentation energy; HOMO–LUMO map; NPA charge.